Scarlets hooker Matthew Rees will make his ninth appearance as captain in a side which also features a return to the international set up for Ospreys backs Andrew Bishop (centre) and Dan Biggar (fly-half) for the first time since before the 2011 Rugby World Cup.
"The Ospreys have been in a rich vein of form and their victory over Leinster last weekend to take the RaboDirect PRO12 title was a boost for the whole of Welsh rugby," said Wales caretaker head coach Rob Howley.
"Dan and Andrew have been playing particularly well and we are looking forward to seeing both players in a Welsh shirt again.
"We have picked a side on form, with an eye on bringing players through for the future, but very much with the intention of getting the summer campaign off to a winning start."
Elsewhere the Ospreys also provide both locks in Ian Evans and Alun Wyn Jones and most of the back row with Ryan Jones (No8) and Justin Tipuric packing down alongside Scarlets blindside flanker Josh Turnbull.
Saracens prop Rhys Gill joins Rees and Jones in the front row to complete the pack.
In the backs, Bishop is joined in the centre by his former clubmate, Perpignan's James Hook, Blues scrum-half Lloyd Williams teams up with Biggar and Dragons wing Aled Brew completes the line-up.
Another potential new cap could be awarded from the bench with Scarlets centre Adam Warren joining soon-to-be centurian Williams. Another Dragons wing Will Harries and Ospreys scrum-half Rhys Webb provide the remaining cover for the backs.
Ospreys hooker Richard Hibbard and regional colleague Paul James provide support for the front row, with Scarlets flanker Aaron Shingler completing the match-day 22.
"We have an opportunity against the Barbarians to get an important summer series off to a winning start," added Howley.
"We have momentum from the RBS Six Nations and the Ospreys have added to that with a great win in our domestic competition.
"We are now looking for the next step and a victory on home soil against a formidable Barbarians team before we set off for Australia."
Ospreys prop Ryan Bevington will remain in Wales as 23rd man for the Barbarians fixture with the remaining 16 players from the 38-man training squad named due to leave for Australia tomorrow (Thursday) to begin preparations for the first Test in Brisbane.
The final members of Wales' tour party, which will total 34 players, will be named at the Millennium Stadium on Saturday immediately after the Baa-Baas fixture, with the team to play the Wallabies in that first match due to be named the following Thursday.
If Williams appears from the bench as expected he will be the first Welsh forward to win 100 caps and join Gareth Thomas (Bridgend/Cardiff/Celtic Warriors/Toulouse) in second place behind Wales' most capped player Stephen Jones (Llanelli/Scarlets/ASM Clermont Auvergne) who has appeared 104 times.
Wales: Liam Williams (Scarlets); Harry Robinson (Blues), Andrew Bishop (Ospreys), James Hook (Perpignan), Aled Brew (Dragons); Dan Biggar (Ospreys), Lloyd Williams (Blues); Rhys Gill (Saracens), Matthew Rees (Scarlets) Captain, Rhodri Jones (Scarlets), Alun Wyn Jones (Ospreys), Ian Evans (Ospreys), Josh Turnbull (Scarlets), Justin Tipuric (Ospreys), Ryan Jones (Ospreys)
Replacements: Richard Hibbard (Ospreys), Paul James (Ospreys), Aaron Shingler (Scarlets), Martyn Williams (Blues), Rhys Webb (Ospreys), Adam Warren (Scarlets), Will Harries (Dragons)